Process for the purification of liquid hydrocarbons.



UNITED STATES, PATENT OFFICE-,1

rnLIz nrcn'rna, or masastasenaaa'mm; GE'nkhnY'.

4 rnoonss iron. was ruaimcarron or Lmu'ni araa caanows.

15098, 764. No Drawing.

mg is a specification,

I have proved .by numerous'ex eriments that while liquids of slightlalka ine character improve the action 0 catalyzers, liq uids containingacid unfavorably affect the catalytic action of such materials asboneblack, blood carbon, charcoal or the particularly active carbonproducedby the dis- Qti-llation of coal with mineral matter con-.taining lime and clay. The deleterious ac- 1 tion of acid liquids isPrcbebly due the promptlabscrption of the acid into the pores of thecatalytic materlal, the acid either destroying or dissolving theexceedingly delicately developed active carbon surface or destroying 'ordissolving the mineral portions which support the active carbon sureofthe enzol seriesand terp'enes, the thor-.

faces. a V

Nearly all liquid hydrocarbons, more particularl cruderock-oilhydrocarbons, those ough purification of which is of great imi-'portance to 1ndustry,v conta1n alread game and mineral acids, or suchac1 s are formed by the action of the air. Hitherto,

, in order to remove such acid contents and thus to bring the catalyzersto the full efliciency, I have utilized, in accordance with myinventionforming the subject matter of myprior application Serial Number593955,

active carbon containing lime. The hi hly divided lime'contained in thesaid car on,

is converted by the calcining process re;- quired for rendering thecarbon active,';into caustic lime which exercisesjalkaline action in theliquid, and has some effect in neutralizin the acid or acids which maybe present with slight quantities of alkaline {lye-,gloy

in the oil. But I have found by continued experiments that considerablybetter, results of. urification can be obtained by pplying, be'f dre thecatalytic treatment, a treatment means of which the acids,partlywithcoiipf ,eration ;of the an"or oxygen -supplieig are convertedinto salts which are absorbed by the active surface without itsstructure be- .ing damaged o'r are brought onthe said surface into athorough contact with the activated oxygen. I

Specification of terms Pa'te'nt. Application flled' September 9,1912.Serial no. 718,437..

at I, Far-11x Rronritn, a.

{or the mixing blower,

ing and filterlng Patented J une 2,- 1 9 14.

The present invention, therefore, consists n the combination of aprocess for purify- 1n g liquid hydrocarbons by mix in same w thfinely-divided 'catalyzers in solid cond1t1on and bringing the mixtureinto labor ougli contact with oxygen containing gases with a preliminarytreatment of the hydro carbons to be purified with alkalinelye. In suchcombined process finely-divided active carbon f any known kind may beused as zcntalzyzin substance such as bonebiack, blood ca on or aboveall, an active carbon obtained by distilling a 'fin'el '-divided mixtureof natural fuels such as t e carbon powder formed by the handling ofcoal in bri queting factories and clay containing mineral matter .suchas fine ashes. Such finely divided carbon is intermixed with thehydrocarbon to be purified and oxygen-containing gas such as atmosphericair is intro duced into the mixture preferably in finelydividedcondition.

In order to avoid the damaging of the finely-divided active carbon bythe purifying action in accordance with this invention the carbon isadded to the hydrocarbon only after a vpreliminary treatment with alkli'ne lye. i

The invention is carried out, for instance in a process for purifyingilluminating oil, in the following manner: 100 liters of crude lightinggp'etroleum are thoroughly mixed for 40 minutes, at ordinarytemperature, with three liters of a 20% NaOH ly,'by mechanical stirringor shaking or by blowing air through the liquidor by both means.The-stirring gear and the admission of air, are then stopped, and

the pil left to stand, the impurities contained in, the lye,.settling onthe bottom fairly soon,

whence they are removed in the usual man ner. In man casesthesubsequent, washof the ithus preliminarily purified'oil is advisable,but not absolutely necessary; A somewhat modified iprocess which, in

most cases renders the washing and filtering i mnecessary, andexercisesa very'favorable influence on the quality-of the oils, consistsin mixing the oi a'fter the lye treatment above described is completed,with-gfinel -di- 'vided ashes, or clay, calcined ,withexclusion of11513) ODWifihSlIIll- (more particularly clay larjnor ani or.- or a nic;substances in ,=the shape .0 fine ow er of high absorptive propertiesand ight weight, in the quantity A of em to- 400 gr. per- 100 mixingcontinuing then for another 2-3 minutes, after which the oil is left tosettle, or is filtered. After this preliminaryt'reatment, the oilseparated from the precipitate or filtrate, is mixed with about 5 kg. ofactive carbon per 100'liters, as described in the prior application, themixing continuing 30-40 minutes and being efiected'by introducing air ina fine spray through perfo; rated ipes or in any other suitable manner,w 'ereb the injurious impurities contained in t e lighting oil, arecompletely separated, and a product excellent in every respect andhaving the greatest illuminating power, is obtained.

urification of crude benzin and benzol is cgjil'ried out in the sameway, only considera for 100 liters only 0.5 liter of a 20% NaOH lye,being needed because. of the naturally smaller quantities of impuritiescontained in the said light hydrocarbons, and in most cases about 2.5-3kg. of active carbon are 'suflicient for carrying out the process.

7 When treating these volatile substances, the

injection of t e air in fine sprays into the liquid must be efiected insuch a manner as to enable such vapors as escape to be evenlongersettling or filtration.

The four comparative experiments given below, show in a striking mannerthe favorable efl'ect of the combined use of alkali and active carbon,there resulting a considerable improvement in the color of the oil, inthe smell of the oil and of the combustion gases, in smallerresinification and consequent carbonization of the wick, in the chimneyremaining bright and, chiefly, in the considerable increase of theilluminating efiect due to these properties. 7

Experiment A.-1O liters of Roumanian crude oil were thoroughly mixed forfifteen minutes with 450 cubic cms. of 66 H 50 The acid tar was thenseparated from the oil; the oil was neutralized with NaOH lye and washedwith water. The color ofthe purified oil was greenish yellow; its smelllike petroleum. Whenburned in alamp the after about half an hoursburning, whereas wick became black, with oformation of scale,

liters of' oil; are

smaller quantity of lye, for instance the chimney after abpuemo' hourslburning e51 showed -a whitish coatin The illuminat- 'ing' power was14.2can es;" T;

oil was treated Ewp "ment B:}The crude as in Experiment A, but after theneutralization, 700 r. of active carbon were. mixed with the 011 for'40minutes by means of an air jet supplying the air in finelydividedcondition; The resulting oil had a greenish Water-like color; its smellwas less stron than -in Experiment A. The lamp wic after two hoursburning, be-

came dark brown, but without any scale while the "lamp chimney showedonly a slight whitish coating after five ,h-ours" burning. The wastegases had a very slight odor. The illuminating power was 15.2 candleswith 14 Bunsen burners as in Experiment A.

Experiment O.10 liters of Roumanian crude oil of the. kind used inExperiments A and B, without subjection tothe preliminary treatment withH,SO, were thoroughly mixed for 40 minutes by means of an air blast with300 cubic cms. of 20% N aOI-I lye, and left to stand for three hours;500 gr, of finely-divided active carbon were then added and the mixingcontinued for 40 minutes with a'supply of finely-sprayed air. The colorof thefr'esulting oil was as clear as crystal, it had a, very slightsmell similar to ether. The lamp chimney, after ten hours burning, wasstill perfectly bright; The wick, after one hours burning, was stillyellowish-white, and only after two hours burning was it colored brownat the outer edge of the gasifying flame, while the inner portionremained yellow and without coating for another six hours. The

waste gases had scarcely any perceptible l smell. The illuminating powerwas 16.5 candles and after ten hours burning 16.2 candles with the sameburner used in Ex periments A and B.

Empem'ment D.10 liters of Roumanian crude lighting oil like'that used inExperiments A, B and C, but not subjected to preliminary treatment withH SO was mixed for 50 minutes with 350 cubic cms. of 25% Na CO and leftto stand for three hours; 700 gr. of active carbon were then added andthoroughly mixed for 40 minutes by a spray of finely-divided air.Theresulting oil had an illuminatin power after ten hours of 16.8candles with the same burner used in Experiments A and B. The otherproperties of the purified oil were almost exactly like that of thepurified oil produced in solid condition and insoluble within the hy-.

drocarbons and then bringing the mixture into thorough contact withoxygen containmg gas.

2. A process for purifying liquid hydrocarbons comprising treating the hdrocarbons with alkaline lye, mixing t e same thereafter with finelydivided active carbon and then bringing the mixture into thoroughcontact with oxygen containing g 3. A process for purifying liquidhydrocarbons comprising treating the h drocarbons with alkaline lye,mixing t e same thereafter with finely divided artificially preparedcarbon containing dry distilled naturally occurring fuels and mlneralmatter and then bringing the mixture into with oxygen containingstances, mixing thereafter the hydrocarbons with finely vided catalyzersinsoluble within the hydrocarbonsand then bringing the mixture mtothorough contact with oxygen containing gas.

In testimony whereof I ailix my signature in presence of two witnesses.

\FELIX RICHTER.

Witnesses JEAN GRUND, CARL GRUND.

